EP0061286B1 - Procédé de préparation de vanadates d'alcoyle - Google Patents

Procédé de préparation de vanadates d'alcoyle Download PDF

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Publication number
EP0061286B1
EP0061286B1 EP82301335A EP82301335A EP0061286B1 EP 0061286 B1 EP0061286 B1 EP 0061286B1 EP 82301335 A EP82301335 A EP 82301335A EP 82301335 A EP82301335 A EP 82301335A EP 0061286 B1 EP0061286 B1 EP 0061286B1
Authority
EP
European Patent Office
Prior art keywords
reaction
heptane
reactor
butanol
product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82301335A
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German (de)
English (en)
Other versions
EP0061286A1 (fr
Inventor
Walter Lee Magee, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stauffer Chemical Co
Original Assignee
Stauffer Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stauffer Chemical Co filed Critical Stauffer Chemical Co
Priority to AT82301335T priority Critical patent/ATE10101T1/de
Publication of EP0061286A1 publication Critical patent/EP0061286A1/fr
Application granted granted Critical
Publication of EP0061286B1 publication Critical patent/EP0061286B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/28—Metal alcoholates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/68—Preparation of metal alcoholates
    • C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups

Definitions

  • the present invention relates to a process for forming alkyl vanadates by the reaction of vanadium pentoxide with an alkyl alcohol.
  • the present invention therefore provides a process of preparing tri-n-butyl or triisobutyl vanadate which comprises heating vanadium pentoxide with n-butanol or isobutanol characterised in that the heating takes place in the presence of heptane which assist removal of by-product water.
  • the reaction is conducted by admixing the desired quantities, as described below, of vanadium pentoxide, n-butanol or iso-butanol, and heptane in the reaction vessel and refluxing the contents of the reactor while maintaining an inert gas blanket over the reaction mixture.
  • the condensed liquid is passed through a trap where a hydrocarbon rich layer will form. Drawing off the water rich layer will remove at least a portion of the water or formation while the remaining liquid (a mixture of the alkanol and heptane) is returned to the reactor.
  • the process can be practiced with a mole ratio of n-butanol or iso-butanol to vanadium pentoxide of from 3:1 to 12:1.
  • the amount of heptane solvent to n-butanol or iso- butanol which can be used ranges from 0.05:1 to 3:1 on a weight basis.
  • This Example illustrates a bench scale synthesis in accordance with the present invention.
  • Vanadium pentoxide (182 g.) was charged into a two liter, three neck vessel equipped with thermometer, a 4 inch (10.16 cm) mechanical stirrer operated at 200 rpm. and Dean-Stark trap condenser.
  • the vessel also contained a mixture of isobutyl alcohol (444 g.) an n-heptane (650 g.).
  • the resulting mixture was heated to reflux under nitrogen.
  • the condensed overhead phase was sent to a phase separator where water was removed, and the organic phase was returned to the reactor. During the first six hours of reflux, about 20 ml. of water was removed. During the next three hours only 3 ml. of water was collected. The reaction was terminated by cooling, and the mixture was allowed to settle.
  • Filtration produced 1518 g. of liquid and a 116 g. filter cake.
  • the filter cake was washed with 170 g. of n-heptane.
  • the liquid phase containing solvents and the desired product was decanted and transferred to a vessel equipped for vacuum distillation.
  • the solvents were stripped at 80-90°C. with the pressure being gradually reduced to 10-20 mm. Hg (0.013-0.026 bar) until no volatiles were collected.
  • the amount of isobutanol and n-heptane that was recovered totalled 918 gm.
  • the triisobutyl vanadate product weighed 250 gm. or 44% of theoretical, based on the weight of isolated product with V 2 0 5 as the limiting reactant.
  • This Example illustrates the preparation of triisobutyl vanadate by the reaction of isobutanol and vanadium pentoxide in the presence of an n-heptane azeotroping solvent.
  • the filtrate containing a mixture of n-heptane, isobutanol, and triisobutyl vanadate product was added to a second reactor and was heated to about 94°C. under application of no vacuum (760 mm Hg. (1 bar)). The solvent was removed, and distillation was continued at about 77°C. and a pressure of 14 mm Hg. (0.018 bar) to complete removal of the remaining solvent. This reactor was then cooled and the triisobutyl vanadate product (28 kg.) was removed. The yield of the product was 25% of theoretical, using the same basis as Example 1.
  • This Example illustrates the preparation of triisobutyl vanadate by the reaction of iso- butanol and vanadium pentoxide in the presence of an n-heptane azeotroping solvent.
  • the filtrate containing a mixture of n-heptane, isobutanol, and triisobutyl vanadate product was added to a second reactor and was heated to about 25°C. under application of slight vacuum (600 mm g.) (0.800 bar). The solvent was removed, and distillation was continued at about 90°C, and a pressure of 15 mm Hg. (0.020 bar) to complete removal of the remaining solvent. This reactor was then cooled and the triisobutyl vanadate product (155 kg) was removed. The yield of the product was 35% of theoretical, using the same basis as Example 1.
  • This Example illustrates the preparation of triisobutyl vanadate by the reaction of iso- butanol and vanadium pentoxide in the presence of a n-heptane azeotroping solvent.
  • Vaccum was applied to a 1920 liter pilot plant reactor, and the vacuum was released with nitrogen. Vacuum was applied again, and the reactor was charged with 573 kg. of iso- butanol and 857 kg. of n-heptane. The vacuum was released using nitrogen, and the agitator in the reactor was turned on. To the reactor was then added 181.5 kg. of vanadium pentoxide. Heating was initiated, and refluxing began at about 85°C. Refluxing was continued, and water by-product formed by the reaction was entrained by the solvents and was periodically removed through a trap. The reaction was allowed to run for approximately 41 hours at a temperature of 88° to 93°C. at the end of which time about 19.5 kg. of water of reaction was collected. The reactor was then allowed to cool to about 30°C. The resulting mixture was filtered to yield a filter cake of unreacted V 2 0, having a weight of about 194 kg. This filter cake was washed with n-heptane and dried.
  • the filtrate containing a mixture of n-heptane isobutanol, and triisobutyl vanadate product was added to a second reactor and was heated to about 85°C. under application of slight vacuum (600 mm Hg.) (0.800 bar). The solvent was removed, and distillation was continued at about 85°C. and a pressure of 14 mm Hg. (0.018 bar) to complete removal of the remaining solvent. This reactor was then cooled and the triisobutyl vanadate product (116 kg.) was removed. The yield of the product was 20% of theoretical, using the same basis as Example 1.
  • This Example illustrates the preparation of triisobutyl vanadate by the reaction of isobutanol and vanadium pentoxide in the presence of an n-heptane azeotroping solvent.
  • the filtrate containing a mixture of n-heptane, isobutanol, and triisobutyl vanadate product was added to a second reactor and was heated to about 75°C. under application of slight vacuum (500 mm Hg.) (0.666 bar). The solvent was removed, and distillation was continued at about 90°C. and a pressure of 20 mm Hg. (0.026) to complete removal of the remaining solvent. This reactor was then cooled and the triisobutyl vanadate product (77 kg.) was removed. The yield of the product was 18% of theoretical, using the same basis as Example 1.
  • Vanadium pentoxide (376 g.), isobutyl alcohol (800 g.) and heptane (100 ml.) were added to a 1000 ml. reactor equipped with heating mantle, Heller mixer, Dean-Stark trap condenser, thermometer and vacuum pump. The mixture was heated and allowed to reflux.
  • the Table given below shows the time of reaction from the beginning of reflux, the amount of by-product water collected as the reaction proceeded during formation of triisobutyl vanadate, and the temperature of the reaction:
  • the yield of product was 33% of the theoretical yield, based on the amount of by-product water evolved using V 1 0 5 as the limiting reactant.
  • Vanadium pentoxide (375 g.), isobutyl alcohol (800 g.), and heptane (100 ml.) were added to a 2 liter round bottom flask equipped with Dean-Stark trap, Heller mixer, thermometer and heating mantle, and the reaction mixture was heated to initiate the reaction. After approximately 8-1/2 hours of reaction a total of 42 ml. of water by-product was collected. The percentage yield was 39% of theoretical, using the same basis as in Example 6.
  • Example 7 The same procedure used in Example 7 was employed with 1125 gm. of vanadium pentoxide, 2400 gm of isobutyl alcohol, and 300 g. of heptane. After approximately 10-1/4 hours of reaction, a total of about 94 ml. of by-product water was recovered. The percentage yield was 30% of theoretical, using the same basis as in Example 6.
  • reaction mixture was allowed to cool and was filtered under a nitrogen tent through a CELITE® brand filter.
  • the respective filter cakes were washed with an appropriate solvent (Run A: 254 g. of heptane and Run B: 201 g. of toluene). Refiltration removed some observed cloudiness in each filtrate.
  • the filtrates were transferred to 2-liter flasks and each was stripped for 2-4 hours at atmospheric pressure to 10-20 mmHg. (0.013-0.026 bar) with the pressure gradually being reduced during the stripping operation to avoid bumping or foaming.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (3)

1. Un procédé de préparation de vanadate de tri-n-butyle ou de triisobutyle qui consiste à chauffer le pentoxyde de vanadium en présence de n-b'utanol ou d'isobutanol, caractérisé en ce que le chauffage se produit en présence d'heptane qui contribue à l'élimination de l'eau formant le sous-produit.
2. Un procédé ainsi que revendiqué dans la revendication 1., caractérisé en ce que le rapport molaire du n-butanol ou de l'isobutanol par rapport au pentoxyde de vanadium est compris dans le domaine de 3/1 à 12/1.
3. Un procédé ainsi que revendiqué dans la revendication 1 ou 1 a revendication 2, caractérisé en ce que la quantité d'heptane par rapport au n-butanol ou à l'isobutanol est comprise dans le domaine de 0,05/1 à 3/1 exprimée sur une base pondérale.
EP82301335A 1981-03-20 1982-03-16 Procédé de préparation de vanadates d'alcoyle Expired EP0061286B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82301335T ATE10101T1 (de) 1981-03-20 1982-03-16 Verfahren zur herstellung von alkylvanadaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US245868 1981-03-20
US06/245,868 US4351775A (en) 1981-03-20 1981-03-20 Method for preparation of alkyl vanadates

Publications (2)

Publication Number Publication Date
EP0061286A1 EP0061286A1 (fr) 1982-09-29
EP0061286B1 true EP0061286B1 (fr) 1984-10-31

Family

ID=22928424

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82301335A Expired EP0061286B1 (fr) 1981-03-20 1982-03-16 Procédé de préparation de vanadates d'alcoyle

Country Status (5)

Country Link
US (1) US4351775A (fr)
EP (1) EP0061286B1 (fr)
JP (1) JPS57169494A (fr)
AT (1) ATE10101T1 (fr)
DE (1) DE3261096D1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465637A (en) * 1982-09-13 1984-08-14 Stauffer Chemical Company Alkyl vanadate color improvement
US4465636A (en) * 1982-09-13 1984-08-14 Stauffer Chemical Company Process for the manufacture of alkyl vanadates
US4452724A (en) * 1982-09-29 1984-06-05 Stauffer Chemical Company Alkyl vanadate color improvement
US5021595A (en) * 1990-03-02 1991-06-04 Exxon Chemical Patents Inc. Transition metal catalyst composition for olefin polymerization

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920751A (en) * 1967-11-28 1975-11-18 Rhone Poulenc Sa Process for the preparation of ethylenic carbonyl compounds
US3657295A (en) * 1970-11-23 1972-04-18 Texaco Inc Preparation of tri-n-butyl vanadate
DE2261386C3 (de) * 1972-12-15 1975-08-28 Ruhrchemie Ag, 4200 Oberhausen Verfahren zur Herstellung von Magnesium und Aluminium-Alkoxiden
DE2342536A1 (de) * 1973-08-23 1975-03-06 Dynamit Nobel Ag Verfahren zur herstellung von vanadiumoxitrialkoholaten
DE2343056A1 (de) * 1973-08-25 1975-03-06 Dynamit Nobel Ag Verfahren zur herstellung von vanadylalkoholaten
US4014911A (en) * 1975-10-16 1977-03-29 Stauffer Chemical Company Method for preparing ethyl vanadate
US4014912A (en) * 1975-10-16 1977-03-29 Stauffer Chemical Company Method for preparing organic vanadates

Also Published As

Publication number Publication date
US4351775A (en) 1982-09-28
EP0061286A1 (fr) 1982-09-29
JPS57169494A (en) 1982-10-19
DE3261096D1 (en) 1984-12-06
ATE10101T1 (de) 1984-11-15

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